Phosphorus esters of 5-amino-1,2,4-triazol-3-ol

ABSTRACT

Triazolyl organophosphorus derivatives of the formula   WHEREIN R1 represents alkyl or cycloalkyl, R2 and R3 each represents hydrogen, alkyl, alkenyl, alkinyl, phenyl, or aralkyl, or together with the nitrogen atom to which they are bonded represent a heterocyclic ring, R4 represents alkoxy, alkylthio, mono- or dialkylamino, R5 represents alkyl, alkylthio, phenyl, phenoxy, mono- or dialkylamino, and X represents oxygen or sulphur, a process for their manufacture, and their use in pest control.

United States Patent [191 Dawes et a1.

[ June 10, 1975 1 PHOSPHORUS ESTERS OF S-AMINO-l,2,4-TRlAZOL-3-OL [75] Inventors: Dag Dawes, Pratteln; Willy Meyer, Basel; Beat Bohner, Binningen, all of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: May 25, 1973 [21] Appl. No.: 364,175

[30] Foreign Application Priority Data June 19, 1972 Switzerland 9113/72 Apr. 18, 1973 Switzerland 5501/73 [52] US. Cl ..260/308 R; 260/247.1 B;

260/2475 E; 424/200 [51] Int. Cl. C07f 9/08; C07f 9/16; C07f 9/24 [58] Field of Search... 260/308 R, 247.5 E, 247.1 B

[56] References Cited .UNITED STATES PATENTS 3,686,200 8/1972 Scherer et a1 260/308 R FOREIGN PATENTS OR APPLICATIONS 713,278 8/1954 United Kingdom 260/308 R Primary Examiner-Alton D. Rollins Attorney, Agent, or Firm-Frederick 1-1. Rabin [57] ABSTRACT Triazolyl organophosphorus derivatives of the formula R N X R 5 5 Claims, No Drawings PHOSPHORUS ESTERS OF S-AMINO-l ,2,4-TRIAZOL-3-OL The present invention relates to triazolyl organophosphorus derivatives, to a process for their manufacture, and to their use in pest control.

The compounds have the formula R -N-II X sents C,-C -alkoxy or C C ,-alkylthio, R repre- P I n R (I) sents C,C alkyl, C,C -alkoxy, or C C alk- N 4 ylamino, and X represents oxygen or sulphur. R N The compounds of the formula I can be manufac- 3 5 tured by the following known methods:

N N -R la) R X l 4\ l R acltl blnding PHal H x m.... 1 S/ R agent 7 I) (III) N II -R lb) R 3? I /IP-Ha1 I lie N R N (II) (IV) wherein R represents alkyl or cycloalkyl, R and R each represents hydrogen, alkyl, alkenyl, alkinyl, phenyl, or aralkyl, or together with the nitrogen atom to which they are bonded represent a heterocyclic ring, R represents alkoxy, alkylthio, monoor dialkylamino, R represents alkyl, alkoxy alkylthio, phenyl, phenoxy, monoor dialkylamino, and X represents oxygen or sulphur.

The alkyl, alkoxy, and alkylthio groups R, to R contain l to 19, preferably 1 to 6, carbon atoms in the chain and can be straight-chain or branched, unsubstituted or optionally substituted by halogen atoms, such as fluorine, chlorine, bromine, and/or iodine.

Examples of such groups include: methyl, methoxy, methylthio, ethyl, ethoxy, ethylthio, 2-chloroethyl, propyl, 3,3,3trichloropropyl, propoxy, propylthio, isopropyl, n-, i-, sec. and tert. butyl, 4-chl0ro-(n)-butyl, npentyl, n-dodecyl, (n)-nonadecyl.

The cycloalkyl groups R have 3 to 8, preferably 5 to 6. ring carbon atoms; exemplary of such groups are cyclopentyl and cyclohexyl.

The aralkyl radical R is preferably a benzyl, phenethyl, diphenylmethyl group or a group of the formula The aralkyl group, in particular the benzyl and phenyl groups, can be unsubstituted or substituted. Suitable substituents at these groups are halogen, preferably fluorine, chlorine, and/or bromine, C C alkyl, C -C,,-haloalkyl, especially CF C C alkoxy,

2 C C alkylsulphinyl, C C alkylsulphonyl, and- /or nitro groups.

Preferred compounds on account of their action are those of the formula I, wherein R represents C,C- ,,alkyl or cyclopentyl, R represents hydrogen, C -C alkyl or allyl, R represents hydrogen, C,-C- -alkyl, allyl, phenyl or benzyl, or R and R together with the nitrogen atom to which they are bonded represent the morpholino or pyrrolidino radical, R repre- In the formulae II to IV the symbols R to R and X have the meanings given for the formula I, Hal represents fluorine, chlorine, bromine, or iodine, but particularly chlorine or bromine, and Me represents a monovalent metal, preferably an alkali metal, in particular sodium or potassium.

The following bases, for example, are suitable as acid binding agents, tertiary amines, such as triethylamine, dimethylaniline, pyridine, inorganic bases, such as hydroxides and carbonates of alkali and alkaline earth metals, preferably sodium and potassium hydroxide.

The reaction may be carried out preferably in solvents or diluents which are inert towards the reactants or in an excess of a tertiary amine, e.g. pyridine. Suitable inert solvents or diluents are, for example, the following: aromatic hydrocarbons, such as benzene, toluene, petroleum distillates, halogenated hydrocarbons, e.g. chlorobenzene, polychlorobenzenes, bromobenzene; chlorinated alkanes with l to 3 carbon atoms, ethers, such as dioxan, tetrahydrofuran; esters, such as ethyl acetate; ketones, such as methyl ethyl ketone, di-

dae, Galleriidae, Culicidae, Tipulidae, Stomoxydae,

Muscidae, Calliphoridae, Trypetidae, Pulicidae, as well as Acaridae of the families: lxodidae, Argasidae, Tetranychidae, Dermanyssidae.

By addition of other insecticides and/or acaricides it is possible to improve substantially the insecticidal or acaricidal action and to adapt it to given circumstances.

The following active substances are examples of suitable additives:

Organic phosphorus compounds Bis-0,0-diethylphosphoric acid anhydride (TEPP) Dimethyl-( 2,2,2-trichloro- 1 -hydroxyethyl phosphonate (TRICHLORFON) l,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED) 2,2-dichlorovinyldimethylphosphate VOS) Z-methoxycarbamyl- 1 -methylvinyldimethylphosphate (MEVINPHOS) Dimethyl-l-methyl-2-(methylcarbamoyl)vinylphosphate cis (MONOCROTOPHOS) 3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DICROTOPHOS) 2-chloro-Z-diethylcarbamoyll -methylvinyldimethylphosphate (PHOSPHAMIDON) 0,0-diethyl-(or S)-2-(ethylthio)-ethylthiophosphate (DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate (THI- OMETON) 0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0,0-diethyl-S-2-(ethylthio)ethyldithiophosphate (DI- SULFOTON) 0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETON METHYL) 0,0-dimethyl-S-( l ,2-dicarbethoxyethyldithiophosphate (MALATHION) 0,0,0,0-tetraethyl-S ,S '-methylene-bisdithiophosphate (ETHION) dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N- formylcarbamoylmethyl)-dithiophosphate MOTHION) 0,0-dimethyl-S-(N-methylcarbamoylmethyl)- dithiophosphate (DIMETHOATE) 0,0-dimethyl-O-p-nitrophenylthiophosphate RATl-llON-METHYL) 0,0-diethyl-O-p-nitrophenylthiophosphate THION) O-ethyl-0-p-nitr0phenylphenylthiophosphate (EPN) 0,0-dirnethyl-O-(4-nitro-m-tolyl)-thiophosphate (FENlTROTl-IION) 0,0-dimethyl-O-2,4,5-trichlorophenylthiophosphate (RONNEL) O-ethyl-O-2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE) 0,0-dimethyl-O-Z,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) 0,0-dimethyl-0-(2,5-dichloro-4-iodophenyl)- thiophosphate (JODOFENPHOS) 4-tert.butyl-2-chlorophenyl-N-methyl-O- methylamidophosphate (CRUFOMATE) 0,0-dimethyl-0-(3-methyl-4- methylmercaptophenyl)-thiophosphate (PENTH- ION) lsopropylamino0-ethyl-0-(4-methylmercapto-3- methylphenyl)-phosphate (DICHLOR- O-ethyl-S,S-

( FOR- (PARA- 4 0,0-diethyl-0-p-(methylsulphinyDphenylthiophosphate (FENSULFOTHION) 0-p-(dimethylsulphamido)-phenyl-0,0-dimethylthiophosphate (FAMPHUR) 0,0,0,0-tetramethyl-0,0'-thiodi-p-phenylenethiophosphate 0-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethylO-(a-methylbenzyl-3-hydroxycrotonyl)phophate 2-chlorol 2,4-dichlorophenyl )vinyldiethylphosphate (CHLORFENVINPHOS) l-chlorol 2,4,5-trichlorophenyl)vinyldimethylphosphate 0-[2-chloro-l-(2,5-dichlorophenyl)]vinyl-0,0-

diethylthiophosphate Phenylglyoxylonitriloxime-0,0-diethylthiophosphate (PHOXIM) 0,0diethyl-0-( 3-chloro-4-methyl-2-oxo-2-H- l benzopyran-7-yl)-thiophosphate (COUMAPHOSI 2,3-p-di0xandithiol-S,S-bis(0,0-diethyldithiophosphate) (DIOXATHION) 5-[(6-chloro-2-oxo-3-benzoazolinyl)methyl]0,0-

diethyldithiophosphate (PHOSALONE) 2-( diethoxyphosphinylimino 1 ,3-dithiolane 0,0-dimethyl-S-[ 2-methoxy-l ,3,4-thiadiazol-5-( 4H onyl-(4)-methyl]dithiophosphate 0,0-dimethyl-S-phthalimidomethyl-dithioph0sphate (lMIDAN) 0,0-diethyl-0-( 3 ,5 ,6-trichloro-2-pyridyl )thiophosphate 0,0-diethyl-0-2-pyrazinylthi0phosphate ZIN) 0,0-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)thiophosphate (DIAZINON) 0,0-diethyl-0-(2-quinoxalyl)thiophosphate 0,0-dimethyl-S-( 4-oxol ,2,3-benzotriazin'3(4H ylmethyl)-dithiophosphate (AZINPHOS- METHYL) 0,0-diethyl-S-(4-oxol ,2,3-benzotriazin-3(4H ylmethyl)-dithiophosphate (AZINPl-IOSETHYL) S-[(4,6-diamino-s-triazin-2-yl)methyl]-0,0- dimethyldithiophosphate (MENAZON) 0,0-dimethyl-0-( 3-chl0r0-4-nitrophenyl)thiophosphate (CHLORTHION) 0,0-dimethyl-O(or S)-2-(ethylthioethyl)thioph0sphate (DEMETON-S-METHYL) 2-(0,0-dimethyl-phosphoryl-thiomethyl)-5-methoxypyrone-4-3,4-dichlorobenzyl-triphenylphosphoniumchloride 0,0-diethy1-S-(2,5-dichl0r0phenylthiomethyl)dithiophosphate (PHENKAPTON) 0,0-diethyl-O-( 4-methyl-cumarinyl-7 )-thiophosphate (POTASAN) 5-amino-bis(dimethylamido)phosphinyl-3-phenyl- 1,2,4-triazole (TRlAMlPHOS) N-methyl-S-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide (VAMIDOTHION) 0,0-diethyl-0-[2 diethylamino-4-methylpyrimidyl- (6)]-thiophosphate (DIOCTHYL) 0,0-dimethyl-S-(methylcarbamoylmethyl)- thiophosphate (OMETHOATE) 0-ethyl-0-(8-quinolinyl)-phenylthiophosphonate (OXINOTHIOPHOS) O-methyl-S-methyl-amidothiophosphate TOR) O-methyl-O-(2,5-dichloro-4-bromophenyl)-benz0thi- (THIONA- (MONI- 5 ophosphate (PHOSVEL) 0,0,0,0-tetrapropyldithiophosphate 3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxycis-crotonamide 0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (ETHOATE-METHYL) ,O-diethyl-S-( N-isopropylcarbamoylmethyl dithiophosphate (PROTHOATE) S-N-( l-cyano-lmethylethyl )carbamoylmethyldiethylthiolphosphate (CYANTHOATE) S-( 2-ac etamidoethyl )-O ,0-dimethyldithiophosphate Hexamethylphosphoric acid triamide (HEMPA) 0,0-dimethyl-0-( 2-chloro-4-nitrophenyl)thiophosphate (DICAPTHON) 0,0-dimethyl-O-p-cyanophenyl thiophosphate (CYA- NOX) O-ethyl-O-p-cyanophenylthiophosphonate 0,0-diethyl-O-Z,4-dichlorophenylthiophosphate (DI- CHLORFENTHION) 0-2,4-dichlorophenyl-O-methylisopropylamidothiophosphate 0,0-diethyl-0-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL) dimethyl-p-(methylthio )phenylphosphate 0,0-dimethyI-O-p-sulphamidophenylthiophosphate 0-[p-(p-chlorophenyl)-azophenyl]0,0-dimethylthio- I phosphate (AZOTHOATE) 0-ethyl-S-4 -chlorophenyl-ethyldithiophosphate O-iosbutyl-S-p-chlorophenyl-ethyldithiophosphate 0,0-dimethyl-S-p-chlorophenylthiophosphate 0,0-dimethyl-S-(p-chlorophenylthiomethyl)dithiophosphate 0,0-diethyl-p-chlorophenylmercaptomethyldithiophosphate (CARBOPHENOTHION) 0,0-diethyl-S-p-chlorophenylthiomethylthiophosphate 0,0-dimethyl-S-(carbethoxy-phenylmethyl)dithiophosphate (PHENTHOATE) 0,0-diethyl-S-(carbofluorethoxy-phenylmethyl)- dithiophosphate 0,0-dimethyl-S-carboisopropoxy-phenylmethyl)- dithiophosphate 0,0-diethyl-7-hydroxy-3 ,4-tetramethylenecoumarinyl-thiophosphate (COUMITHOATE) 2-methoxy-4-H-l ,3,2-benzodioxaphosphorin-2- sulphide 0,0-diethyl-0(5-phenyl-3-isooxazolyl)thiophosphate 2-(diethoxyphosphinylimino)-4-methyl-l ,3-

dithiolane tris-( 2-methyll -aziridinyl )-phosphine oxide (METEPA) S-( 2-chlorol -phthalimidoethyl )-0,0-diethyldithiophosphate N-hydroxynaphthalimido-diethylphosphate dimethy- 1-3,5,6-trichloro-2-pyridylphosphate 0,0-dimethyl-0-(3,5,6-trichloro-2-pyridyl)thiophosphate S-2-(ethylsulphonyDethyl dimethylthiophosphate (DlOXYDEMETON-S-METHYL) diethyl-S-2-(ethylsulphinyl)ethyl dithiophosphate (OXIDISULFOTON) bis-0,0-diethylthiophosphoric acid anhydride (SUL- FOTEP) dimethyl-l,3-di(carbomethoxy)-l-propen-2-y1- phosphate dimethyl-(2,2,2-trichloro-1-butyroyloxyethyl)phos- 6 phate (BUTONATE) 0,0-dimethyl-0-(2,2-dichloro-l-methoxyvinyl)phosphate bis-(dimethylamido)fluorphosphate (DIMEFOX) 3 ,4-dichlorobenzyl-triphenylphosphoniumchloride dimethyl-N-methoxymethylcarbamoylmethyldithiophosphate (FORMOCARBAM) 0,0-diethyl-O-( 2,2-dichlorol -chloroethoxyvinyl)- phosphate 0,0-dimethyl-0-( 2 ,2-dichlorol -chloroethoxyvinyl phosphate O-ethyl-S,S-diphenyldithiolphosphate O-ethyl-S-benzyl-phenyldithiophosphonate 0,0-diethyl-S-benzyl-thiolphosphate 0,0-dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphate (METHYLCARBOPHENOTHION) 0,0-dimethyl-S-(ethylthiomethyhdithiophosphate diisopropylaminofluorophosphate (MIPAFOX) 0,0-dimethyl-S-(morpholinylcarbamoylmethyl)dithiophosphate (MORPHOTHION) bismethylamido-phenylphosphate 0,0-dimethyl-S-(benzenesulphonyl)dithiophosphate 0,0-dimethyl-(S and O)-ethylsulphinylethylthiophosphate 0,0-diethyl-0-4-nitrophenylphosphate triethoxy-isopropoxy-bis(thiophosphinyl)disulphide 2-methoxy-4H-l ,3 ,2-benzodioxaphosphorin-2-oxide octamethylpyrophosphoramide (SCHRADAN bis-(dimethoxythiophosphinylsulphido)- phenylmethane N,N,N,N-tetramethyldiamidofluorophosphate (DIMEFOX) O-phenyl-O-p-nitrophenyl-methanethiophosphonate (COLEP) O-methyl-O-(2-chloro-4-tert.butyl-phenyl)-N- methylamidothiophosphate (NARLENE) 0-ethyl-O-( 2 ,4-dichlorophenyl )-phenylthiopho sphonate 0,0-diethyl-O-( 4-methy1mercapto-3 ,5-

dimethylphenyl)-thiophosphate 4,4-bis-(0,0-dimethylthiophosphoryloxy)-diphenyl disulphide 0,0-di-(l3-chloroethyl)-0-(3-chloro-4-methylcoumarinyl-7 )-phosphate S-( 1 -phthalimidoethyl )-0,0-diethyldithiophosphate 0,0-dimethyl-0-(3-chloro-4- diethylsulphamylphenyl)-thiophosphate O-methyl-O-(2-carbisopropoxyphenyl)-amidothiophosphate 5-(0,0-dimethylphosphoryl)-6-chlorobicyclo( 3.2.0)-heptadiene( 1,5) 0-methyl-O-(2-i-propoxycarbonyll -methylviny1)- ethylamidothiophosphate. Nitrophenols and Derivatives 4,6-dinitro-6-methylphenol, sodium salt [Dinitrocresol] dinitrobuty1phenol-(2,2,2 )-triethanolamine salt 2-cyclohexyl-4,-dinitrophenyl [Dinex] 2-1-methylheptyl)-4,-dinitrophenyl-crotonate [Dinocap] 2-sec.butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl] 2-sec.butyl-4,-dinitrophenyl-cyclopropionate 2-sec.butyl-4,6-dinitrophenylisopropylcarbonate [Dinobuton] Miscellaneous pyrethrin l aldoxime) O-Z-diphenyl-N-methylcarbamate 2-(N-methylcarbamyl-oximino)-3-chlorobicyclo[2.2. l lheptane 2-(N-methylcarbamyl-oximino)- bicyclo[2.2l ]heptane 3-isopropylphenyl-N-methyl-N-chloroacetalcarbamate 3-isopropylphenyl-N-methyl-N-methylthiomethylcarbamate O-(2,2-dimethyl-4-chloro-2,3-dihydro-7- benzofuranyl)-N-methylcarbamate -(2,2,4-trirnethyl-2,3-dihydro-7-benzofuranyl)-N- methylcarbamate O-naphthyl-N-methyl-N-acetal-carbamate 0-5 ,6,7 ,S-tetrahydronaphthyl-N-methyl-carbamate 3-isopropyl-4-methylthio-phenyl-N- methylcarbamate 3 ,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate v3-methoxymethoxy-phenyl-N-methylcarbamate 3-allyloxyphenyl-N-methylcarbamate 2-propargyloxymethoxy-phenyl-N-methyl-carbamate 2-allyloxyphenyl-N-methyl-carbamate 4-methoxycarbonylamino-3-isopropylphenyl-N- methyl-carbamate 3,5-dimethyl-4-methoxycarbonylamino-phenyl-N- methyl-carbamate 2-7-methylthiopropylphenyl-N-methyl-carbamate 3-(a-methoxymethyl-Z-propenyl)-phenyl-N-methylcarbamate 2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate 4-(methyl-propargylamino-3,5-xylyl-N-methylcarbamate 4-(methyl-y-chloroallylamino)-3,5-xylyl-N-methylcarbamate 4-(methyl-B-chloroallylamino)-3,5-xylyl-N-methylcarbamate 1-( ,B-ethoxycarbonylethyl )-3-methyl-5-pyrazolyl- N,N dimethylcarbamate 3-methyl-4(dimethylamino-methylmercaptomethyleneimino)-phenyl-Nmethyl-carbamate l,3-bis(carbamoylthio )-2-(N,N-dimethylamino)- propanehydrochloride 5,5-dimethylhydroresorcinoldimethylcarbamate 2-[ ethyl-propargylamino]-phenyl-N- methylcarbamate 2-[methyl-propargylamino]-phenyl-N- methylcarbamate 4-[dipropargylamino]-3-tolyl-N-methylcarbamate 4-[dipropargylamino]-3,5-xylyl-N-methylcarbamate 2-[allyl-isopropylamino]-phenyl-N-methylcarbamate 3-[allyl-isopropylamino]-phenyl-N-methylcarbamate Chlorinated Hydrocarbons y-hexachlorocyclohexane DAN; 'y I-ICH] l,2,4,5,6,7,8,8-octachloro-3a,4,7,7a

4,7-methylene indane [CHLORDAN] l,4,5,6,7,8,8-heptachloro-3a,4,7,7oz-tetrahydro-4,7-

methylene indane [HEPTACHLOR] 1,2,3 ,4, l O, l O-hexachlorol ,4,4a,5 ,8,8a-hexahydroendo-l ,4-exo-5,S-dimethanonaphthalene [AL- DRIN] 1,2,3 ,4,10,10-hexachloro-6,7-epoxyl,4,4a,5,6,7,8,8a-octahydro-exo-l ,4-endo-5 ,8- dimethanonaphthalene [DIFLORIN] l ,2,3.4,10,10-hexachloro-5,7-epoxyl ,4,4a,5,6,7.8,8a-octahydro-endo-endo-S,8- dimethanonaphthalene [ENDRIN] [GAMMEXANE; LIN- -tetrahydro- In addition to the properties cited hereinabove, the compounds of the formula I also display activity against representatives of the division Thallophyta. Thus a number of these compounds display bactericidal action. But they are active above all against phytopathogenic fungi which belong to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes. The compounds of the formula I also evidence a fungitoxic action against fungi which attack the plants from the soil. Further, the new active substances are also suitable for freating seeds, fruit, tubers etc. to protect them from fungus infections. The compounds of the formula I are also suitable for combating plant pathogenic nematodes.

The compounds of the formula I may be used as pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions, in the conventional formulation which is commonly employed in application technology. Mention may also be made of cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take, and be used in, the following forms:

Solid forms:

Dusts, tracking agents, granules, coated granules, im-

pregnated granules and homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, S10 granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/liter to 600 g/liter can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product. i

To these mixtures can also be added additives which stabilise the active substance and/or non-ionic, anionic and cationic surface active substances, which, for example, improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having to ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Suitable carriers are, for example, those mentioned for the solid forms of application. lnsome cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulphonic acid, in addition, alkylaryl sulphonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salts of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with the additives cited hereinabove, in such a manner that, the size of the solid particles does not exceed 0.02 to 0.04 ,u. in wettable powders, and 0.03 1.1. in pastes. To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above, organic solvents, and water are used. Examples of suitable solvents are: alcohols, benzene, xylene, toluene, dimethyl sulphoxide, and mineral oil fractions which boil between 120 and 350C. The solvents must be practically odourless, not phytotoxic, and inert to the active substances.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substances, or several active substances of the general formula I, are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils, singly or in admixture with each other, can be used as organic solvents.

The content of active substance in the above described agents is between 0.1 to in which connection it should be mentioned that, in the case of application from aircraft or some other suitble means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows:

Dusts The following substances are used to manufacture a) a 5% and b) a 2% dust:

5 parts of active substance 95 parts of talcum 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground. Granules The following substances are used to produce 5% granules:

5 parts of active substance, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3 0.8 mm).

ble powder:

a) 40 pans of active substance,

5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid. b) 25 parts of active substance,

45 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture 1:1

parts of sodium dibutyl naphthalene sulphonate, .5 parts of silicic acid,

5 parts of Champagne chalk, l parts of kaolin.

parts of active substance. parts of isooctylphenoxy-polyoxyethylene-ethanol, parts of Champagne chalk/hydroxyethyl cellulose mixture (lzl), parts of sodium aluminium silicate, parts of kieselguhr. parts of kaolin. parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration. Emulsifiable Concentrates The following substances are used to produce a) a and b) a emulsifiable concentrate:

The following constituents are used to prepare a 5% spray:

5 parts of active substance, I part of epichlorohydrin, 94 parts of benzine (boiling limits l60- 190C).

EXAMPLE 1 0 The residue is purified by chromatography on a silica gel column with chloroform 3% methanol as eluant.

The compound of the formula a) 10 parts of active substance, (LUC. H "NQN 3.4 parts of epoxidised vegetable oil. 25 j I S 13.4 parts of a combination emulsifier consisting I! A ffttlhllllh'd-lklir liufioilt cllclfniiilf d y 40 parts of dimethylformamide, N 43.2 parts of xylene. b) 25 pans of active substance, is obtained as a yellow 011; m, 1.5010.

i g g z z g g alcohol The following ccompounds are also obtained in analpolyglycol ether mixture. ogous manner: 557 5 pans of dirnethylformamide.

pa so xy ene Rl N N X From these concentrates it is possible to produce, by R I H R B dilution with water, emulsions of any desired conceno 4 tration. R N R Spray 3 5 P1 l D t a a R R R R R X! 1ys1c a I 2o (1. 11 (1) cu. 0H 00 11 0 0 11 s 11 1 ,4889

r r J CH CH CH 06 11 OL H S 11 l ,499J

20 T t CH CH GL OQ H OC H O o 1 ,4672

- 20 CH CH CH OCH OCH S 11 l 5O 61 20 CH CH CH. OC H C 11 S o 1 ,4980 i 20 1 CH CH CH OC H SC H Q) 5 n 1, +985 20 CH. CF 0 H n 1 +706 CH 5 1 5 SCjH7(I) O D g i 20 CH CH. 0H 00 711 .11. ...,(1) s 11 1 51/0 r 011 ca 00 -1 0c u s n 1 5281 g 7 CH3 CH (EH 0 OC H 00 11 s 11 1 51-5 Continued p 11 l l {y I Pi1y s i c nl ll'1t1: i! n? I H?) l L c H (j) H H c H o H n 1 5120 c n (1) ca 011 o ca "1- o H 00 a s n 1 5267 57 "2 '2 '2 2 53-5 1) a a 20 0 11, (1) c11 011 c1. c-. 1 00 11 1.) 11 1,5189

D 0' 1 cu 0c 1* 0c 11 s 11 1 5021 1 R X Physical Data 7 r I T Y (4 1 ,0 11 (1) 011 -011 CH2 011 -011 01- 09 11 00 11 0 5 1,5051

F (1 1 (1) 011 01 CH2 CH CH CH2 OC2H5 00 11 s 11 I7 20 0 11 H 011 00 11 00 11 s n 1,5162 c 11 (1 H 011 00 11 SC3H (n) s n 1,4968 6.) H CH 00 11 11 s n= 1,4531

q t 20 (3 15(1) c11 011 (x 11 C3H7(nj 3111 1,4752 0 5 (1) H CH3 00H ocii s ng 1,5231 0 11 61) c11 c11 00 11 1111011 3 ni 1,5047

m 0 (1. 11 (1) 011 (:11. 0011 01,11 3 ti 1,4170

2o 0. 11 (1) 11 CH3 00 11 s 11 1,5642

20 c 11 CH3 @11 00 11 (K1 1i s 11 1,4956

EXAMPLE 2 era littoralis, I-Ieliothis and Leptinotarsa decemlineata.

B. Systemic Insecticidal Action To determine the systemic action, rooted bean plants (Vicia fabae) were put into a 0.01% aqueous active substance solution (obtained from a 10% emulsifiable concentrate).

After 24 hours, aphids (Aphis fabae) were placed on the parts of the plant above the soil. The aphids were protected from contact and gas action by means of a special device. The test was carried out at 24C and relative humidity. In the above test the compounds according to Example 1 displayed systemic action against this fabae.

EXAMPLE 3 7 Action Against Chilo Suppressalis Six rice plants at a time of the variety Caloro were transplanted into plastic pots (diameter at the top 17 cm) and reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L: 34 mm long) took place 2 days after the active substance had been applied in granule form to the paddy water (rate of application: 8 kg of active substance per hectare). Evaluation of the insecticidal action took place days after application of the granules.

The compounds according to Example 1 were active in the above test against Chilo suppressalis.

EXAMPLE 4 Action Against Ticks A) Rhipicephalus bursa Five adult ticks or 50 tick larvae were counted into a glass tube and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from an emulsion series each containing 100, 10, l and 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and placed on its head, so that the active substance emulsion could be absorbed by the cotton wool. In the case of the adults evaluation took place after 2 weeks, and in that of the larvae after 2 days. Each test was repeated twice.

B. Boophilus Microplus (larvae) Tests were carried out in each case with OP- sensitive larvae using an analogous dilution series as in the case of test A. (The resistence refers to the tolerability of Diazinon).

The compounds according to Example I acted in the above test against adults and larvae of Rhipicephalus bursa and sensitive and OP-resistent larvae of Boophilus microplus.

EXAMPLE 5 Acaracidal Action Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture of Telranyclms urlic'ae placed on them 12 hours before the test for the acaricidal action. The mobile stages which have migrated were sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth did not run off. The number of living and dead larvae, adults and eggs were evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the interim, the treated plants were kept in greenhouse compartments at C.

The compounds according to Example 1 were active in the above test against eggs, larvae and adults of Tetranychus urticae.

EXAMPLE 6 Action Against Soil Nematodes To test the action against soil nematodes, the active substance (in the concentration indicated in each case) was applied to, and intimately mixed with, soil infected with root gall nematodes (Meloidgyne avenaria). Immediately afterwards, tomato cuttings were planted in the thus prepared soil in a series of tests and after a waiting time of 8 days tomatoes were sown in another test series.

In order to assess the nematocidal action, the galls present on the roots were counted 28 days after planting and sowing respectively. The compounds according to Example 1 displayed good action against Meloidgyne avenaria.

What is claimed is:

1. A compound of the formula R N-N 2 I I X 4 \N o n/ wherein R represents C -C alkyl or cyclopentyl; R represents hydrogen, C -C alkyl or ally]; R represents hydrogen, C C alkyl, allyl, phenyl or benzyl; or R and R together with the nitrogen atom to which they are bonded represent morpholino or pyrrolidino; R represents C -C alkoxy or C,C allkylthio; R represents C,-C alkyl, C C alkoxy, C -C alkylamino or phenyl; and X represents oxygen or sulphur.

2. A compound according to claim 1, of the formula 3. A compound according to claim 1, of the formula (1)0 1 S u o1 (oo 11 P (OC H (CH3) 2N 5) 2 5. A compound according to claim 1 of the formula 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1, of the formula
 3. A compound according to claim 1, of the formula
 4. A compound according to claim 1 of the formula
 5. A compound according to claim 1 of the formula 